Process of treating petroleum oil



R. CROSS.

PROCESS OF TREATING PETROLEUM OIL.

APPLICATION FILED MAY 2, 1921.

1,423.500, Patented July 18, 1922.

career castes.

UNHTED stares soy onoss, or KANSAS CITY, MISSOURI, assrcnoa 'ro easo'nmnraonuors corarams,

1NC., OF NEW YORK, N. Y A CORPORATION OF NEW YORK.

PROCESS OF'TREA'IIIYG PETROLEUM OIL.

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Continuationof application Serial No. 211,407, filed January 11, 1918.

Serial No. 466,119.

To all whom it may concern Be it known that I, ROY CRoss, a c tlzen of the United States, residing in the city of .Kansas City, county of Jackson, and State Among the salient objects of the invention 'are to provide aprocess in which the heat,

which is transmitted to the oil in the heating zone, is conserved and maintained in the body of the oil until such time as the oil has had an opportunity to react or'attaln a substantial equilibrium under the cracking temperature and pressure to which it is subj ected; to provide a process in which the decomposition or reaction of the oil in the reacting zone produces an increased pressure, which assists in raising the boiling point of the oil and thereby promoting the decom position of the oil; to provide a process that can be operated continuously and one that affords a more; completeconversion of the oil body in that the temperature is not materially decreased in the reacting zone by such endothermic react-ions as vaporization and radiation to provide a process in which certain of the gases produced by the process, having a 'critical temperature below the cracking temperatureof the charging stock, are intermittently or continuously removed from the reactingzone soas to prevent an excessive or unnecessary pressure in said reacting zone; to provide'a process which isv economical of operation in thatthe heat ismore or less retained in the oil body during decomposition of the oil itself; to provide a process in which the heat from the gases and oils discharged from the reacting zone is utilized-to preheat the fresh charging stock, which action also serves to cool such oil and Specification of Letters Patent.

. temperature.

liquid phase is passed to a'r'eacting zone- PatentedJully is, 11.922.

This application filed ma a, 1921.

gases and, in general, to provide an improved process of the character referred to.

The accompanying drawing shows a view partly 1n side elevation and partly in vertical section of an apparatus for carrying out the invention. a 4

In the present' invention the oil to be treated 1s fed continuously through a heat- 1ng zone as, for example, through a continuous coil of pipe seated in a suitable furnace and there heated to the desired reacting The oil then in substantially which may take the form of an'enlarged chamber which is insulated from radiation and maintained under the same pressure as the oil in the heating zone. This pressure 18 maintained substantially uniform in both the coil tube and the reacting chamber 3 by reason of the accumulated gases in the upper part of the reacting chamber. The oil" having been heated to a cracking temperature in the heating zone continues to reactwhile in the reacting zone, such reaction taking place substantially-in the liquid phase due to the high pressure maintained, although there will be formed some gases which may be such as methane, ethane, pentane, hexane,

and other substances having a critical temperature below the cracking temperature of the oil under treatment. In other words, certain gases as formed by the cracking of the oil and should be removed from the system to prevent undue rise of pressure. There may also be entrained with these gases some small amount of condensable vapors, The bulk of the oil will be removed after the cracking reaction in the form of liquid or in a liquid phase. c This process is in no'wise to be confused with the many distillation processes for cracking oil in which the light hydrocarbons are removed from the cracking zone in the form of vapors.

In the cracking of various kinds of oil, the pressure and temperature used will Vary. For example, in the cracking of a mid-continent gas oil a pressure of 7 50'pounds per square inchv has been found advantageous lwith an oil temperature of 701F800 degrees I I Refer"v ug to the drawings1 designates a furnace in which are mountedthe heating tubes 2 through which the oil is passed. These tubes 2 may take the form of a continuous coil of tour-inch pipe and may for example, be composed of, say, sixty tubes each twenty feet long. From the heating tubes the oil passes to the reacting chamber 3, whlch may take the form of a horizontal shell suitably supported as shown at 3' and insulated as shown at 4:. This shell may take the form of a horizontal cylinder forty feet long and thirty inches in diameter. The apparatus should be capable'of withstanding the desired pressure as, for example 750-1000 pounds, if so high a pressure is used. The oil passes in a substantially liquid condition through the insulated conduit 6 from the coil 2 to the chamber 3. Oil is supplied to thecoil 2 through the feed line, 7 having control valve 8 connected to the feed pump 9. At one end the reacting chamber 3 is provided with an incondensable'gas outlet 10 controlled by throttle valve 11 and with liquid draw-off pipes 12 and 13 controlled by throttle valves 14 and 15 respectively. The treated oil containing a large quantity of gasoline and other low boiling point products may be given a distillation treatment, if

desired, after which treatment the light oils are separated from the heavy residuum and precipitated carbon and the purified light oils such as fuel oil may be' introduced with fresh oil to the system for treatment. The gases accumulating in the reacting chamber may be removed continuously or intermittently, it being necessary, however, ineach instance that sufficient gases be retained within the upper partof said reacting chamher to exert a pressure which will serve to cause the oil to reassume its equilibrium. It will likewise be understood that while the gases that have the critical temperature below the boiling point of the main body of oil, largely consist of incondens'ible gases, although of course certain other gases of the oil which are condensible may mix therewith. .The various pipes 10, 12 and 13 connect to a manifold pipe 16 leading to the coil 17 of a heat, 'interchanger 18. The lower end of the coil is connected by pipe 19 to suitable receiver or storage tank 20. Raw oil is supplied to the pump 9 through the line 21 leading to any suitable source of charging stock. Q The raw oil'is then passed through the heat interchanger 18 where it is preheated by the hot oil and gases passing through the coil 17 and thence delivered by insulated line 22 to the inlet pipe 23 of the charging pump 9. Suitable thermometers 24, 25 and pressure gauge 26 may be provided as well as the burner 27 for the furnace. lt-will be-appreciated that the oil after being subjected to the cracking temperature in the coil 2 is transferred tothe reacting chamberB, which as before stated, is

insulated, and in this chamber the oil is subjected to a pressure exerted thereon to per mit the same to reassume an equilibrium.

For example, Kansas gas oil as it passes through the heating coil may be heated to a temperature of, say, 750 degrees F. more or less and the pressure gradually raised in the heating coil and reacting chamber to say, 750 pounds per square inch. When this oil while at the temperature above definedis maintained in the reacting chamber under a pressure of 750 pounds per square inch by means of certain gases evolved from the oil no substantial vaporization of the: heated oil takes place, the bulk of the oil reacting or cracking in a liquid phase, in which condition it is withdrawn as treated oil from the reacting chamber. The small quantity of the evolved gases which have a critical temperature below 750 F. maintain the high pressure on the reacting oil in its liquid phase and are discharged with the treated oil in such quantities as to always maintain a pressure in the reacting chamber suiiicient to prevent vaporization of the bulk of the oil. It is apparent that if a high pressure is not maintained in the reacting chamber the bulk of the oil heated to this cracking temperature would vaporize, as commonly occurs in all distillation processes that must not be confused with this process which utilizes pressures always sufficiently high to prevent substantial vaporization of the oil. The level of the oil in the reacting chamber may be maintained to about the height of the pipe 12 and the pressure regulated by the withdrawal of the gases having a critical temperature below that of the cracking temperature. The oil through the system and about 30% of the oil Wlll be converted into gasoline, more or less depending on the character of the raw oil being treated.

In an apparatus of the character referred to, the oil may be satisfactorily cracked to the extent indicated b remaining in the apparatus not to excee say, twentyminutes from the time'it enters the heating coil until it leaves the reacting chamber. It is to be understood that the process is a continuous one and I wish to emphasize that the bulk of the gasoline and hydrocarbons formed at all times remains in liquid phase by reason of the conditions under which it is treated and substantially the bulk of the light hydrocarbons formed are removed from the system'in liquid phase, It, is, of course, to be understood that gases are formed which should be removed from the system, as stated, and also that some small of gasoline may either be entrained 'out with the gases or removed as vapor but nevertheless such vaporization is to be prevented as far as possible and is a rather incidental and inconsequential result of the operation of the process.

is fed continuously amount lit is well known in the art that in ordin- 4. A continuous process for treating oils ary distillation processes the vaporization under pressure without distillation consist? and reflux condensation which takes place ing in passing the oil in a relatively small in such processes results in a very large stream through a heating zone where the heat .loss which is eliminated in the present oil is heated to a cracking temperature, in process. transferring the oil while at a cracking tem- I claim as my invention: perature and in a substantially liquid phase 1. A continuous process of treating oil from-the heating zone to an enlarged insuunder pressure without substantial distillalated reacting chamber located outside of tion consistingin passing oil in a relatively the heating zone, in maintaining the oil in small stream througha heating zone where the heating zone, and while in the enlarged it is heated to acracking temperature, in insulated reacting chamber under a substanpassing the oil in a substantially liquid tially uniform pressure of evolved gases of phase while at a. cracking temperature to the oil, said pressure being sufficient to prean enlarged insulated reacting chamber 10- vent any substantial vaporization of the cated outside of the heating zone where furbulk of the oil, and in continuously removther cracking takes place, in maintaining ingtreated oil and gasesfrom the reacting both the insulated reacting chamber and the chamber without returning said oil to the heating zone under pressure of evolved heating zone for retreatment.

gases of the oil that have a critical temperature below the cracking temperature, of the without substantial distillation, which conbulk of the oil said pressure being sufficient i s in pas ing the oilin a relatively small to prevent substantial vaporization of the oil, stream through a heating zone to be heatedand in continuously removing said gases and to a cracking temperature and thence to an the bulk of the treated oil in liquid phase enlarged insulated reacting chamber While from said reacting chamber. the oil is at a cracking temperature, in

2. A continuous process of treating oils maintaining the oil under pressure of under pressure without substantial distillaevolved gases while in the heating zone and tion, consisting in passing the oil in a relathe enlarged reacting chamber, which prestively small stream through a heating zone sure is suflicient to prevent a substantial where the oil is heated to a cracking temvaporzati'on of the bulk of the oil in the perature, in discharging the oil from the heating zone and the reacting chamber durheating zone in a substantially liquid phase lng conversion of the heavier hydrocarbons and at a cracking temperature to an enlarged into increased quantities of lighter hydroinsulated reacting cham of the heating zone where further cracking larged insulated reacting chamber gases and takes place, maintaining the oil in both the oil without again passing said discharged enlarged insulated reacting chamber and the oil through the heating zone. heating zone under pressure of evolved gases k of the oil having a critical temperature bestantial distillation consisting in passing low the cracking temperature of the bulk the oil in a relatively small stream through of the oil, said pressure being always sufa heating zone to be heated to a cracking ficient to prevent any substantial vaporizatemperature, and thence to an enlarged intion of the oil, and in continuously removsulated reacting chamber, in maintaining ing the bulk of the oil in liquid phase and the oil in the heating zone and in the enaid pressure ga e fro id eacting larged reacting chamber under a pressure chamber. of the evolved gases of the oil sufiicient to 3. A continuous process for treating oils prevent any substantial vaporization of the under pressure Without substantial distillaoil during conversion of the heavier hydrotion consisting in passing the oil in a relacarbons intoj increased quantities of lighter liquid phase from the heatin tivelysmall stream through a heating zone hydrocarbons" while in theheating zone and where the oil is heated to a cracking te'mthe enlarged reacting chamber, and in disperature, in transferring the oil while at a charging oil andgases from the enlargedincracking temperature and in a substantially sulated reacting chamber without again -inlarged insulated reacting c amber located zone. a outside of the heating zone, in maintaining 7- process of cracking o l without subthe oil in the heating zone, and while in the stantial d stillation, comprising continuenlarged insulated reacting chamber under ously passing oil in a small stream through pressure of evolved gases of pressure. being suflicient to prevent any subtemperature and then to an enlarged instantial vaporization of the bulk of the oil,- sulated reacting chamber, in Sub ectmg the and in continuously removin treated oil o l while in the heatlng zone and in the enand gases from the reacting chamber withlarged insulated reacting chamber to a presout distillation of said oil.

6. A process of cracking oil without sub-' the oil, said a heating zone to be heated to a cracking 5. A process of cracking petroleum oil F ber located outside carbons, and in discharging from the enzone to an entroducing the discharged oil to the heating sure of evolved gases of the oil having a all:

critical temperature below the cracking temperature, said pressure being sufficient to prevent substantial vaporization of the oil, in removing treated oils and gases from the enlarged insulated reacting chamber, and in collecting the treated oils without again passing said oils through the heating zone.

8. A continuous process of treating petroleum oils without substantial distillation, consisting in passing the oils in'a relatively small stream through a heating zone and raising the same to a cracking temperature, directing the oil therefrom to a-relatively large insulated reacting chamber and there maintaining the oil under sufiicient pressure ofevolved gases of the oil having a critical temperature below the cracking temperature of the bulk of the oil to prevent vaporization of the cracked hydrocarbons, introducing additional fresh oil to the heating zone, and drawing ofi the cracked liquid oil from the insulated reacting chamher without recirculation of the same through the heating zone while maintain ing the temperature and pressure condition su stantially uniform.

9. A continuous process of treating petroleum oil without substantial distillation consisting in passing the oil in a relatively small stream through a heating zone where it is raised to a conversion temperature, in introducing the oil to an enlarged insulated reacting zone and there maintaining the oil under'pressule of the evolved gases of the oil to prevent vaporization of the heated hydrocarbons, in continuously Withdrawing from the enlarged reacting zone suliicient cracked liquid oil and gases to maintain a constant level therein and'uniform temperatures and pressures on the system and simultaneously introducing regulated quantities of fresh oil to the heating zone.

10. A continuous process of treating petroleum oil without substantial distillation, consisting in passing the oil in a relatively small stream through a heating zone where it is raised to a cracking temperature under a substantial pressure, then passing the oil to an enlarged insulated reacting zone and there permitting it to collect in a pool while maintaining the oil under pressure of the evolved gases of the oil having acritical temperature below the cracking temperature to prevent vaporization of the hydrocarbons, introducing fresh oil to the heating zone and drawing off cracked oil from the insulated reacting zone while maintaining the temperature and pressures through the system relatively constant. 7

11. A process of converting heavy petroleum hydrocarbons of substantially the same series without substantial distillation, consisting in bringing the hydrocarbons to a cracking temperature in a heating zone during the continuous passage of the Hydrocar- ,soo

bons in a comparatively small stream.

through said zone, then passing the oil to an enlarged insulated reacting zone where no heat is applied, and in maintaining it in a relatively greater body in said reacting zone, the oil in both zones being subjected to presure of the evolved gases of the oil having a oil in a small stream continuously through a heating zone to be heated to a cracking temperature, in then discharging the oil into an enlarged insulated reacting chamber wherein a substantial quantity of the heated oil accumulates, in maintaining the oil while passing through the heating zone and when in the enlarged insulated reacting chamberunder pressure of evolved gases of said oil, said pressure being suiiicient to prevent substantial vaporization of the bulk of the oil that is at a temperature above the cracking temperature, in withdrawing from the" enlarged reacting chamber treated oil and pressure gases, and in collecting thetreated oil without returning said oil to the heating zone for retreatment. I

13. A process of converting petroleum hydrocarbons without substantial distillation consisting in directing the oil in comparatively small streams through the heating zone and raising it to a conversion temperature, passing the oil to an enlarged insulated reacting zone and there collecting it in a relatively greater body, permitting the oil to reassume an equilibrium-therein by maintaining sufficient pressure upon the oil by evolved gases of the oil having a critical temperature below the cracking temperature of the main body of this oil to prevent 'any substantial vaporization, and in drawing off oil and a portion of the pressure gases from the enlarged reactin treatment of said Wit drawn oil.

14. A process of converting petroleum hydrocarbons without substantial distillation lit chamber without reconsisting in directing" the oil in comparatively small streams through the heating zone and raising it to a conversion temperature; passing the oil to an enlarged insulated reactm Relative y greater body permitting the oil to reassume an equilibrium therein without the addition of heat to the reacting chamber by maintaining suficient pressure thereon by zone and there collecting it in a evolved gases of the oil having a crictical temperature below the cracking temperature of the bulk of the oil to prevent any substantial vaporization, Withdrawing the oil from the reacting chamber Without retreatment thereof in the heating zone, and adding fresh untreated oil to the heating zone.

15. The process of continuously treating hydrocarbon oils Without substantial distillation, which consists in introducing oil to a heating zone where the oil is heated in a rel atively small stream to a cracking tempera-- ture, and in thence discharging the same to an enlarged insulated reactingchamber, in

maintaining the oil under pressure of evolved gases while in the heating zone, and the enlarged insulated reacting chamber, which pressure is sufficient to prevent a substantial vaporization of the bulk of the heated oil in the heating zone and the reacting chamber during the conversion thereof, and in Withdrawing treated oil and some of the pressure gases from the enlarged insulated reacting chamber Without again returning said Withdrawn oil to the heating zone for retreatment.

ROY CROSS. 

